Separation of methylacetylene from c4 hydrocarbons



Mmmh zfl, 1945. w. s. WALLS ET AL 2,371,860

r SEPARATION OF METHYLAGETYLENE FROM C4 HYDROCARBONS Filed Dec. 16, 1943 C3 HYDROCARBONS CONTAINING METHYLACETYLENE FEED STOCK 7 6 {CAHYDROCARBONS CONTAINING METHYLACETYLENE) FRACT IO NATING COLUMN PROPANE C4HYDROCARBONS FREE FROM METHYLACETYLENE INVENTORS W.S. WALLS MR. DEAN Patented Mar. 20, 1945 UNITED Y STATES." FATE SEPARATION OF METBYLACETYLENE FROM C4 HYDROCARBQNS ing methylacetylene from C4 hydrocarbons and especially from butadiene or from butadienecontaining mixtures oi"C4 hydrocarbons or C1 and C4 hydrocarbons. As used herein the term butadie'nefis used in its usual sense to designate 1,3-

butadiene.

Rubber synthesis requires a butadiene product not only of high purity (that is containing a maximum percentage of butadiene), but also as tree as possible of traces of materials deleterious to the synthesis operations or to the quality of rub ber produced. In certain processes for the manuiacture of butadiene, such as the catalytic dehydrogenation of normal butenes, smallquantities of acetylenes often are formed and appear in the products of reaction. 'Ther volatility of' certain of these acetylenes is such that they may increase to an undesirable concentration in the finished butadiene product unless suitable steps are taken for their removal during the process of separating the butadiene from the other hydrocarbons present in the reaction products. v

Methylacetylene has given particular diilicultyf as an impurity in butadiene. It has been extremely diiilcult and frequentlyfimpossbile to' remove completely this Ca acetylene from the butadiene product. The preparation of butadiene free from any trace of methylacetylene where, as is almost invariably the case; this material is presentin the crude butadiene-containing mixture fed to the purification system, has therefore been a very serious problem. This is unexpected since it would be anticipated from a consideration of the number of carbon atoms and the boiling points and volatilities of the several hydrocarbons in pure form that all of the methylacetylene could be easily separated from the C4 hydrocarbons'by simple fractional distillation. Thus pure methyl acetylene boils at --'9.6 F. while the boiling points of the C4 hydrocarbons commonly encountered range upwardly from 10.8 F.

The reason why removal of methylacetylene presents such a problem is somewhat obscure.

While we do no wish to be limited by any theory we believe that this difliculty may be attributable to the changing relative volatility of methylacetylene with varying composition ofhydrocarbons, r

of parafiin,-olefin, and diolefin types, or to the formation of an azeotrope or azeotropes between the methylacetylene and one or more of the C4 hydrocarbons present which azeotrope or azeotropes boil so close togbutadiene that separation by ordinary fractional distillation is very difflcult or impossible.

ration of most of the Ca hydrocarbons :fromthe: C4 hydrocarbons in a depropanizing columrrrymhis operation, as practiced heretofore, does not-efieet removal ofall the methylacetylen'e. The methyl:v

acetylenenot removed in this operation passes through the succeeding steps'for separationv oii-Gij. hydrocarbons and appears in the butadieneprogi: not. In the second purification step the- 041133: drocarbons from the bottom of the .depropanizing. :1. column are passed to a furfural absorbing column ,4 v. where the n-butane, isobutane, isobutylene' ,andx part of the-butenes-z are removed overhead. The kettle product contains the butadiene, C4 acetyl-,.; I ones," the remainder of the butenes-2 and the methylacetylene which was not takenout in the depropanizing step. The iurfural,. kettle prod-- not is then stripped, the hydrocarbons driven on being passed to a Iractionating column where the butadiene is separated from the butenes-2 and C4 acetylenes. Due to the relatively high solubility of methylacetylene in furfural; the methyl-. .7

acetylene which is not removed in the depropanizing column remains with the butadiene in the furfural kettle product and then passesoverhead with the butadiene in the fractional distillation step, thus, appearing in the final butadiene product.

An object of this invention is to provide an 1m proved method of separating methylacetylene from C4 hydrocarbons; Another object is to pro vide a methodfor more easily and more completely separating methylacetylene from C4 hydrocarbon mixtures containing butadiene. Anotherobject is to provide a method for more easily and more completely removing methylacetylene from butadiene such as concentrated butadiene which falls to meet the specification with respect to methylacetylenecontent. "Another object is to provide a processot the foregoing type which is especially adapted to batchoperation for use as an analytical or laboratory method whereby accurate analysis of a hydrocarbon mixture comprising butadiene'and methylacetylene can be conducted or for use wherever it is desired to rev,

move methylacetylene from butadiene or from a butadiene-containing mixture of C4 or C3 and C4 hydrocarbons.

ables the absolutely complete removal of methylacetylene; Another object is to provide soon- One process for separating the butadiene from C3 and C4 hydrocarbons containing, in addition to butadiene, paratlins, olefins and acetylenes is carried out in severalsteps none. of which utilize this invention. The first step involves the sepatinuous method of the-ioregoing'type. Another object, is to provide a method of separating methylacetylene from Ciracetylenes. .Another object "is to provide a method of separating methyla'cet ylene from other aliphatic C4 hydrocarbons such as butanes and butenes. Numerous other objects a will hereinafter appear. V

The accompanying drawing portrays diagram-.- matically a preferredarrangementof equipment" p a wise Another'object is to provide a' batchwise method of the'foregoing type'which enior carrying out the present invention in. that embodiment wherein operation is continuous.

, We have-now found that methyiacetylene can be more completely removed from Cs hydrocarbons by iractionally distilling the mixture in the presence of propane preferably in sumcient amount to take overhead a major proportion or substantially all or the methylacetylene in admixture with the propane and any other C: hy-

' drocarbon present, usually entirely propylene,

while the C4 hydrocarbons more nearly-or completely free of methylacetylene form the bottom Y product.

We havediscovered that propane increases the relative volatility oi methylacetylene in butadiene containing mixtures substantiall above its normal volatility in such mixtures. Our invention takes advantage or this discovery and effects re moval oimethylacetylene by fractionally distilling in the presence of propane whereby a minimumboiling azeotrope-between the methylacetylene and propane is taken overhead freeing the bottoms product from methylaoetylene. In this way the methylacetylene is prevented from appearing in subsequent steps applied tothe buta'diene or butadiene-containing bottom product and the butadiene product is enabled to meet specifica- The behavior of propane in this respect accordance with the present invention gives a" noticeable improvement in the degree of separation of methylacetylene. the use of larger amounts gives still better results. Where it is feasible the use of propane in amount sumcientto form the azeotrope with substantially all or all of the methylacetylene is'preferred. The use of such an amount of propane as to remove all the methylacetylene overhead is very feasible in a laboratory or batch distillation but may not be feasible in a continuous operation because it may require use of a column of excessive size to accommodate the large amount of propane required to separate completely the methylacetylene.

The present invention may be carried out either continuously or batchwise. The batch operation is often preferred since use of a small and feasible amount of propane in such an operation eflects complete removal or the methylacetylene whereas in a continuous operation the same amount of propane does not effect so great a degree of removal. However, since the application of the invention to an existing continuously operating system for handling butadiene-containing mixtures effects a marked improvement in the extent of methylacetylene removal. it is not intended to imply that it would be advisable to convert such a continuous system to batchwise operation.

Since no fractionating equipment can separate a component completely from the next higher boiling component, it is impossible 'by present fractionating methods to separate methylacetylene completely from the next higher boiling components namelyflthe C4 hydrocarbons. Due to the great diiliculty'cr impossibility of determining quantitatively by present methods methylacetylene in the presence oi Ci acetyienes. a method whereby methylacetylene can be easily These are the preferred conditions in carrying a separated from the CA hydrocarbons is of great .tion of an adequate amount of propane in accordance with the present invention enables all of the methylacetylene to be removed overhead before all of the propane is taken out of the distillation column, thus allowing an absolutely complete separate of methylacetylene from the C4 hydrocarbons, whereas in the absence of the propane some methylacetylene would stay with the C4 hydrocarbons. Thus, in the case of an analytical distillation, the present invention makes possible in an easy manner t q n i tive determination of methylacetylene' insuch a mixture and enables one to quantitatively distin-, guish between methylacetylene and C4 aeetylenes which is difllcult by other known procedures, as is evidenced by the fact that most if not all speciilcations and analyses report simply "acetylen'es (as vinyl acetylenel." Likewise in the case of a batch distillation this embodiment of the invention enables the complete removal of methylacetylene from the C4 hydrocarbons containing butadiene with a minimum-of propane without allowing any of C4 hydrocarbons to go in the methylacety'lene containing cut or vice versa.

In a batch operation the amount of added propane will depend upon the amount of methylacetylene and the completeness of removal which is desired. It will also vary slightly with the pressure. However it may be stated in general that at least 7 mols of propane per mol of methylacetylene should be present at the start. At a pressure of 322.5 pounds absolute this amount of propane effects complete removal or the methylacetylene. As the pressure is lowered somewhat higher mol ratiosof propane to methylacetylene may be required for complete removal of methylacetylene. For exampl at atmospheric pressure 14 to 15 mols of propane per mol of methylacetylone may be required at the start to give complete removal. The amount of propane required-may depend somewhat upon the composition of the ditions from 6 to 19 volumes of propane are required to remove 1 volume of methylacetylene and a minimum number oftrays is required for the depropanizing or fractionating column.

out this invention as applied tolaboratory or batch distillation operations. With thisconcentration of propane present the separation of methylacetylene from C4 hydrocarbons in batch distillation is as easy as-or easier than the separation of propane from C4 hydrocarbons. This volatility behavior of methylacetylene is different from what would be: expected on the basis of the centration, even to Very high propane -oonoentre1- I 9 I sma am u t 1 EP DMI 981 'sumoient propane, to enable, the,b.vifleble. tie} stock compositions Vthat'ean be handledin a given me feed'trayj" 1 mol ercenvpm yieneandc maximifiorpei normal. boiling mini: 0 C? "in w n Gs hm: em i ew t litheenewin i' h re f l c nw ch hdb nii zina s cqn'qnq e w i contin ously-1mm a 's t qeein qf propen an? 1.9 i} h t egbb om oti eicoiu n; an o i n b id in vr q mns s in f he 165. dropa bmi m i e nic cm mu u m a d a mean v'riu i l jthe. C eh dr carbwie" ei iwl hfir nibrmfl tylene ----+f-- i i 1'" i i ng e P mn ip imWi' meem i Butene-l r 20:1 polntf feer'f'the' pqwq -'o n" 'e umnjegmh that 1,3-Butadiene' I H 7 23,9' iii ut evira yyorj h p dpaneeoes bfit man not i i'm -i-r-f' '---'+--f x t biqd i t 11* h s b ob ffhii vie'qi Butene-Z' low thatithe lessjthe U onntpfjpropene goihg-oht m the bottomsphemoieoonipleige the-removal x r me acwl ne j aua i; h 1 m? of propanefvinjeotionWiilbe izvlvotor 'hre new olatility of mefl ylaoetflene '(hpthefpi'efe red m g tice oi, the presentinvention); greatiy feoilitatca the operation or a oepro'panizing oi'ira'otioneting" column. Since the volatility of methylaoeiylene' k, increases gradually with inoreaee iii-propane ooh. I preterm tiona, it may be desirable in practioeiojddonly propanizin'g or "firactionating'colnmn itbppbdu l A a v n ,f mantier described in preceding Paragraph is methyl aoetylene.

' i, v m fm f fi wfi viil fim 5 In continuous distilletion focesses, siioh aein meat an i i m fl ii mm th? l mef i theseparetion of Ca and. Cf hydrocarbons 'in-[a at h we"; m 3 19 @929 depmpamz n oo1iimn,the benefit-e m'b obtaineefj i fib heiw if by the addition ofpropone, are dependent upon -3 9 P m 'i 9'?" gl i p m i P the position at which the p openeis'inJeotedinto #9 m 1%? h n 9 m??? w en ii e iee asa the dep 'opanizing column and'also on the 'elotive since 1? e fl i ,9- hFF 19 h? i e 2 5 amounts of propane to certain C4 hydroe'erbone. P i' FK F 99954??? present in the sectionoithe ooii mnjinto-yvhichr 11mm 7 j j propane is injected., In B'ener'aloihe rei mve QQ XF WQ QW WF 9 F n 99, volatility; of methy1aoet'y1ene,in"thebase of'the tb im si1w x z fqeb ry e ween -al depropenizin'g coliunn'where'ci oleflns',ldioiefl ns pi p v i r with 991 3 3 r z P and c; acetylenes usually predominate, mow and 7' m i h f m 91 8911 f increases gradually With-inbzedizeinpioziano con; 1 Y the d? ;=,vp?*19 l;." 9P, oentretion; the maximum; effect being obtained pmq s" 5 1 I when the ratio oi Propane to C4 hydrocarbons 49 i q t P i 9 mimwmli reaches a high value and the'hydrooerbon com)? "I at h h n Q W QPWRWJP' a??? position is predominately propane; Due to'the descnbgd is e r i i i i e qv r large. emoiint of propane requir ei'lflto be injeo'fied" at v 'i fl iifi fi 'l i m9 to enable ax mum increase inttne-remivevo a: Pane, 91- Q j iih v flii 1 F .Bfiflil tilityoi methyiacetyl ene, it'is usually pi efe'rreflffl h a at t Pm i F9 not to 'seek to obtain the highest Tre1etivevo1atility' an FWFP 'P W 1$1i #WFWFWH??? for the methylacetylene. "It ispreferredto injeotfj jremoval fmethylace tylene the propane at a suitable point below? the '!eed T Pressure at whlch eithelfihe batch 9 con? tray and only in sumcien't omountstdenable'the mmous i i fa m} h 93 dim YY8 9 W given de ropanizing'comninjtdooerete'wprovidejao h P 3 mi y'dr pfi i ifiw iqi butadiene'ofsumoientlylow n ethylacetylenecom Wm, 39? fli qsph rm i 50'n-5 =t he tenttomeet desired specifications TIiepreSencef W 9?! ,Sfifliiifl qQi1i 9hii r of propane in emonnts relativelyrsimill with m njq' h r eii v flw "i spectito C4 hydrocarbons, but IargefWithi'es'pectf j g ti 'b' f TI tomethylacetylene,ser'vesisoincrease'iherehitiveiszs 'f volatility of the methylaoetylene and facilitates Propeneflwaeeddedio "inixtu of.

JCiand 04 its separation'from theC; hydrocarbonsfoontsin-I hydrocarbons containing neiahylaoetylehfi L ing butadiene. l diene,' and c ec i mnes; giving 23.7 liters I ma The process of adding propanetothedepropan teriel havingfgthe tollowing nelys izing eoiumn greatlyinoreases'the'renge'ot feed-iwdepropanizing column and the rengejof OODdi time under which a given depropanizing column lifethylacjetyjm I j canbe operated to obtain satisiactory -emoval ofimethylacetylene from C; hydrocarbons contain-05' fii igm ingbutadiene. v Other Ci'shndhea v The propaneiipreferablyihjectedinto the-dc 1'; A Y I H i a propanizing-columnat some point belowtheifeecl' The 'aboveinixtur was: plaq dlitiithg ket e o I tray, although some beneflciaii'esults caniie ob Podbieiniak Heligridf aotiona ting eolninn-and tained by injecting 'the propane into the column 1 beipchaciis'ii ileo lat! hhnosPhe'ribf-hifegiii 'Ihe; with'the' feed or at some 'point a few trays abo'ye first ihi'ee liters takeh overheadfyvere abouii90 The preferred type of commudfis ammo}; inf oent iheihylaceiy leh'e. The inetliyl'goet yleneioon voives continuously feeding the methylacetyiene" centrapion ihiqheoverhead increased 'rel'pidlywit containing and -butadieneconteining'nnxtu -eet 1| increese i iptopahe'eonoenpi etion enh efi 'rjliters" propane. At 9'liters overhead the Lproductfcon-T" tained 5.9 mol per cent mol per cent propane. The concentration of methylacetylener and. 83

methylacetylene thenstarted to decrease rapidly and at 12.5 liters the productcontained 0.9'mol per cent methylacetylerie andtQ'I 'inol percent propane. The methylacetylene concentration contlnuedgto decreaseuntil at"18.5 liters overhead the product contained'982 mol percent propane I and opl yjofiii 'mol'per cent methylacetylena 'Ihe l and of. the propane temperature plateau w'av en-.

tained' immediately after reaching the" Cr teniperature plateau contained only, C4. unsaturates directshleaty change with the overhead and the resulting vaporized propane fed intothe liq'uid'in' 'storage Whi1e this modification has been def scribed with reference to removal ofmethylacefi ylene from 'butadiene it is applicable to any C4 hydrocarbon or hydrocarbon mixture contami nated with methylacetylenesuch as butenes, bu? .tanes, C4 acetylene's; either singly or in admixture;

1f desired theoverhead C3 hydrocarbons, usually H 0 traction or gas scrubbing with aselectivesolvent countered at l9.7 liters overhead, Samples ob- I and aboi1t,"0,05f mol per cent of acetylenes Atl 22.3 litersoveriiead the .Ci acetyle'nes were 0.1 4 I mol per centandat 22.8'liters overhead were'ao moi per cent." Thus it 'will be seen that an absoe;

lutely clean-separation between methylacetyle'ne and the hydrocarbons was' effectedl by means of the propane.

Theiinvention isnot limited to cases where the C4 hydrocarbon comprises or consists ofQbutadiene'butis applicable broadly to separation of;

methylacetylene from any C4 hydrocarbon. or. mixture of C4 hydrocarbons such as n-butane,-

isobutan, butene-1 butenes-2,fisobutylene butadiene, vinylacetylene or ethylacetylene. either singly or in any combination. It is especially ap propane residue which-is conveniently recycled as I the source of thepropane added in accordance with the present invention; Such asolvent may be furfu'ral.

p In the accompanying drawing the feed containing at least 'onealiphatic C4 hydrocarbon and" methylacetylene passes continuously via line I into frac'tionating column 2. Heat is supplied by the usual reboiler 3. Propane is fed'in continuously via line 4 at apoint not far from the bot tom ofcolumn 2. The Ca'overhead leaves via-line 5 and, after "coolinginthe usual way toat least I partially condense'the samapasses to refiux acpllcable to the separation of mthylacetylene f from butadiene andjrom C4 acetylenes,

The; process of, the present invention ma applied tobutadienecontaminated with methyla acetylene, the mixture consisting. of butadiene,

and methylacetylene constituting .the feed to the methylacetylene overhead and-leave a kettle gaseous phase or m'ay comprise both liquid andgaseous phases depending uponthe' extent of concolumn and the distillation being carriedout, in the presenceof-an amount oi added propane suf e product consisting of pure butadiene and nearly a V or completely free frorn methylacetylene. Where batch distillation is practiced the bottoms are completely free from methylacetylenegln the case of continuous operation,;it is substantially free...-

Thepresent invention may be employed in a batchwiseembodirnent to effect the removal of methylacetylene "from buta diene in storage as in a tank car storageptanlg, spheroid storage tank or thelike by connecting a fractionating column to the storage container by a line to the vapor space therein and a lineto-the -liquid space and passing propane continuously into the liquid in the storage tank whereby vapors; of propane,

' methylacetylene and some butadiene pass through the vapor line into'ithe fractionator where'the butadiene is separated from the Cas and returned via the liquid line to the storage. Among advantagesof thistype of procedure are that the storage vessel functions as the kettle of the fraction atorithe butadiene is cleaned up in storage, and 1 the butadiene is enabled tomeet specifications."

Another advantage isthat if there is sufficient i tlmeaa fractionating'column having only a small capacity can be employed. Another advantage is that such a method; entails substantially only the refrigeration,requirements alreadyin use on the storage facilities since' the already existing refrigeration system: is simply transferred from 5 the topiof the -spheroidor other container to the top OiQthB fIaQtJQHZLtQIE "In, fact no increasein Y refrigeration requirements is involved if 'the in:

coming propane is brought in as a liquid in incumulator' ii from which liquid condensate is returned as reflux via line I while C3 hydrocarbons containingpropane and methylacetylene,

together with propylene if present in the feed, are

withdrawn via line 8; The material withdrawn via line 8 is often in liquid phase but may be in densation; Abottoms fraction containing all the Cg. hydrocarbonspresent in'the feed and more nearly orcompletely free from methylacetylene is withdrawn continuously via line 9.

Fromthe foregoing, it Will be seen carbons, including butadiene. The batch distillation process makes possible'the preparation of butadiene absolutely vfree from 'methylacetylene and the continuous process enablesvproduction of nearly methyla'c'etylenefree butadiene even though the feed contains such a quantity of this tion involves no disadvantages over prior practicesfwhich were incapable of achieving'thefre. suits attainable by the practice of the present invention. i

The t erm's batchf batchwisef' and continuone as used herein have their ordinary meaning a Thus: the terins batch or batchwisel denote a distillation wherein the entirepcharge is placed :in the kettleof the fractionating column and the bottoms product is either allowed to accumulate and withdrawn after the distillation is completed or is, distilled stepwise and the overhead collected a in several sequential fractions kept separate from 1 one another. 'Ihe term f continuous designates a process wherein theCr or C; and C4 l ydrocarbon :feed is charged continuouslyto theiractionator and the overhead and bottoms product a are withdrawn continuously and simultaneously. Weclaim; a a 1. 'I'he vprocess from a C4 hydrocarbon which comprises fracconsisting of propane, propylene and methylac'et-' yieneialthough in some circumstances 'pro'pylenel may be absent, may be subjected to solvent ex-' that the present invention provides a simple feasible method for insuring practically complete or com-'- plete removal of methylacetylene fromct hydro- "5r, methylacetylene: v

' was tionally t said vz methylace'tylene" in the presence or propane :i and ing propaneland methylacetylene. and'forming' a t i ydrocarbon bottom product comprising the C4 content of the mixture.

2; The 'process of. =efiecting aseparation 1 taming said C4 hydrocarbon-andmethylacetylfine thereby taking overheadcahydrocarbons ificludrf 1 tween methylacetylene and C4 acetylenes which comprises fractionally distilling a hydrocarboni mixture containing methylac'etylen'e' and at least one ct-acetylene -in the presence of propam'r'and'=' thereby talringoverhead cz l'iydrocarbons includingpropane and inethylacetylene and forming a bottom product comprising the C4 hydrocarbon content or "the mixture and containing the C acetylene content thereofg 1 3. The process of effecting removal of methylacetylenefrom a C4 hydrocarbon containing thesame which comprises fractionally distilling in a batchwise manner a charge or said C4 hydrocarbons and methylacetylene in the presence oi propane in amount sufllcicnt to take overhead all 01 said methylacetylene in admixture with propane and thereby forming a kettle product comprising the C4 hydrocarbon and entirely iree from methylacetylene.

4. The process or removing methylacetylene from a C4 hydrocarbon containing the same which comprises iractionally distilling the mixture of said Cihydrocarbon and methylacetylene in a batchwise manner in the presence of propane in an amount suiilcient to give a mol ratio of propane to methylacetylene of at least 7 to 1, removing overhead all of the methylacetylene in admixture with propane, and forming a bottoms product comprising said C4 hydrocarbon and completely free from methylacetylene'.

5. The process of removing methylacetylene from a C4 hydrocarbon containing the same which comprises fractionally distilling the mix ture of said C4 hydrocarbon and methylacetylene in a batchwise manner in the presence or propane in an amount sufficient to give a mol ratio of propane to methylacetylene of at least 10 to i, removing overhead all of the methylacetylene in admixture with propane, and forming a bottoms product comprising said C4 hydrocarbon and completely free from methylacetylene.

6. The process of removing methylacctylene from a C4 hydrocarbon containing the some which comprises fractionally distilling the mix ture of said C4 hydrocarbon and methylacetylene in a batchwise manner in the presence of propane in an amount sufilcient to give a'mol ratio of propane to methylacetylene of at least is to l, removing overhead all of the methylacetylene in admixture with propane, and forming a bottoms product comprising said G4 hydrocarbon and completely free from methylacetylene.

7. The process of removing methylacetylene from a Ca hydrocarbon containing the same which comprises continuously feeding the nine 'ture containing said Cs hydrocarbon and methyh to a'fractional'distlllation column at .anintermediate point-thereinand iractionating same continuously injecting propane into said column mols of propane :per mol Iota methylacetylene. in

theliquid m: the column-at the-point of injection; a. j

continuously'rem'oving an overhead iractioncontaming propane and. substantially all. to! the]; i methylac'etylene. containedtin the feed, and con-- tinuously removing a bottom-fraction containine stantially free from methylacetylene.

9;"The process of removing methylacetylene 1 comprises talisman; feeding ,tiifii ixture tbs- 4 theClhydro'carbon content of the feed and sub-i front-acs-hydrocarboncontaining thesame'which' comprises continuously ieeding the mixture con-' taining said C4 hydrocarbon and methylacetylene to a fractional distillation column at an intermediate point therein and ira'ctionating same, continuously injecting propane into-said column at a point adjacent the bottom of said column in an amount such as to give a ratio of at least 10 mols of propane per mol of methylacetylene in the liquid in the column at the point of injection, continuously removing'an overhead traction containing propane and substantially all or the 1 from a C4 hydrocarbon containing the same which comprises continuously feeding the mixture conmethylacetylene contained in the teed, and contaming said Cd hydrocarbon and methylacetylene to a fractional distillation column and fractionating same therein, continuously injecting propane into said column at a point adjacent the bottom of said column, the point of injection of said propane being slightly above the bottom of said col umn and so located that substantially no propane goes out in the bottom product, continuously withdrawing from the top of said-column a G: overhead comprising inethylacetylene and pro pane, and continuously withdrawing from the bottom or said column a bottom traction comprislog the C4 hydrocarbon content of the feed and.

or substantially reduced methylacetylene content. ii. The process oi eiiecting removal of methyl-,

7 actylene from a Csihydrocarbon containing the v same and butadiene which comprises iractlcnally distilling in. a batchwise manner a charge of said Q4 hydrocarbon and methylacetylenein the presence of propane in amount sufllcient to take overhead all of saidmethylacetylene in admixture with propane andthereby forming a kettle product comprising the G4. hydrocarbon amen.

tirely free from methylaeetylene. 12, The process removing methylactylene V trom a C4 hydrocarbon containing thesam'e and vbutadiene which comprises continuously feeding the mixture containing said Cs hydrocarbon and log propane into said column at a point adjacent of said column a bottoms fraction comprising the C4 hydrocarbon content of the feed and of substantially reduced methylacetylene content,

. 8. The process of removing methylacetylene from a C4 hydrocarbon containing the same which neethylacetylene to a fractional distillation col umn and fractionating same therein, continuously injecting propane into said column at a point adjacent the bottom 0! said column, continuously withdrawing from the top of said columnaC; overhead comprising methylacetylene and propane, and continuously withdrawing from the bottom or said column a bottoms fraction comprising the C4 hydrocarbon content 01 the feed and of substantially reduced methylacetylene conten l I 13. The: process 7 of; removingmethyla'cetylene from a- C4 hydrocarbon mixture containing: butadiene and methylaoetylenez which comprisey fractional!!! distilling said mixture'in thepresence or propane in amount ambient to taker-at least the major portion of the -methylacetylene over head; removing overhead C3; hydrocarbons in-- eludingv thepropane 1 and at least a major. portion of the .methylacetyienez contained.- in saidmixture, and forming" a; bottom product; comprising them hydrocarbon content; of: the: mixinture-- and. nearly ireeiromi methylacetylne; 7

14; The process of; removing; methylaoetylne fromahydrocarbonmixture containing. Ci hydro-- carbon inciudingrbutadiene; and: also containing? propylene and methylacetylene which. comprises i'racti'onaily distilling said mixture inthespresence:

of propane, in amount suficienrto-tako at least the major portion: of the methy1acety1ene:overaav'meo hour, remuvinr overhead" 63* hydrocarbons includinz thez-propane-an'diat least rmajorrportion;

of the? methyiacetyine contained"v in said: mix

tux-e;v and forming a bottom prm'iuct comprising: the Ci hydrocarbon content. of the mixture. and near-i1 tree; from methyiacetylenea:

15; The process of'anaiyticany dtennininmti ier methylacetyiene'contentofa gampiemfiCiandEi hydrocarbonsi momma; r'xi'tliylacetyiitese andat 1 leastvroneci iacetyiene whicl iicompris'as;iractlcm=- a-liyi'diatiliinzfsaid:sampl in a batc-hwise manner in --thepreaencosot 'propazi'ei in: amountmorertham aumcient to overhea'di all y or," said metiivi acetylene:- in; admixture with propane-5113mm? ai l 1 of said; methyiacetylna: overhead; in' ammxmm 

